The present invention relates to novel catalysts which significantly improve the bleaching effect of hydrogen peroxide in the treatment of textile material without causing any substantial damage to fibre and dyeings, and to washing and cleaning agent formulations comprising these catalysts as well as to a method for cleaning and/or bleaching substrates which uses such washing and cleaning agent formulations.
Peroxide-containing bleaches have been used for some time in washing and cleaning processes. At a liquor temperature of 90xc2x0 C. or more they are highly effective. As the temperature drops, however, their performance decreases markedly. It is known that diverse transition metal ions, added in the form of suitable salts or co-ordination compounds containing such cations, catalyse the degradation of H2O2. In this way it is possible to increase the bleaching effect of H2O2, or of precursors releasing H2O2 and also of other peroxide compounds, which effect is insufficient at lower temperatures. Important in practice are in this case only those combinations of transition metal ions and ligands, the peroxide activation of which is also expressed in an enhanced readiness to oxidise with regard to the substrate and not only in a catalase-like disproportionation, for the latter activation, which is unwanted in the present case, can further diminish the bleaching effects of H2O2 and its derivatives, which are insufficient at low temperatures.
As regards bleaching-effective H2O2 activation, mono- and polynuclear variants of manganese complexes with diverse ligands, in particular with 1,4,7-trimethyl-1,4,7-triazazyclononane and, optionally, oxygen-containing bridging ligands, are held to be particularly effective at present. Such catalysts are sufficiently stable under practice conditions and contain the ecologically safe metal cation Mn(n+). However, their use entails substantial damage to dyes and fibres. The catalysts of this invention, however, are capable of significantly increasing the bleaching effect of H2O2 without causing any substantial damage to the washing goods.
Accordingly, this invention relates to a washing and cleaning process, which comprises adding to the liquor comprising a peroxide-containing washing and cleaning agent 1-500 xcexcmol per litre of liquor of a compound of formula 
wherein
n is 0, 1, 2 or 3,
m is 1, 2 or 3,
R4 is hydrogen or linear or branched C1xe2x80x94C4alkyl,
R8 is hydrogen or linear or branched C1xe2x80x94C4alkyl,
Y is a linear or branched alkylene radical of formula xe2x80x94[C(R4)2]rxe2x80x94, wherein r is an integer from 1 to 8, and the R4 groups have each independently of one another the meaning given above;
xe2x80x94CXxe2x95x90CXxe2x80x94, wherein X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)amino,
xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94, wherein R4 has the meaning cited above, and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula: 
or a 1,2-aryl radical of formula 
wherein R9 is hydrogen, SO3H, CH2OH or CH2NH2, 
R and R1 are each independently of the other cyano, halogen, OR4 or COOR4, wherein R4 has the meaning cited above, nitro, linear or branched C1-C8alkyl, linear or branched partially fluorinated or perfluorinated C1-C8alkyl, NR5R6, wherein R5 and R6 are identical or different and are each hydrogen or linear or branched C1-C12alkyl, or linear or branched C1-C8alkyl-R7, wherein R7 is NH2, OR4, COOR4 or NR5R6, which have the meanings given above, or xe2x80x94CH2xe2x80x94N⊕R4R6R7 or xe2x80x94N⊕R4R5R6, wherein R4, R5 and R6 have the meanings cited above, R2 and R3 are each independently of the other hydrogen, linear or branched C1-C4alkyl or unsubstituted aryl, or aryl which is substituted by cyano, halogen, OR4 or COOR4, wherein R4 is hydrogen or linear or branched C1-C4alkyl, by nitro, linear or branched C1-C8alkyl, NHR5 or NR5R6, wherein R5 and R6 are identical or different and are each hydrogen or linear or branched C1-C12alkyl, or by linear or branched C1-C8alkyl-R7, wherein R7 is NH2, OR4, COOR4 or NR5R6, which have the meanings given above, or by xe2x80x94N⊕R4R5R6, wherein R4, R5 and R6 have the meanings given above.
It is preferred to add 5 to 350 xcexcmol, preferably 10 to 250 xcexcmol, per litre of washing liquor, of a compound of formula (1) or (2) to the washing and cleaning liquor.
If, in the compounds of formula (1), R and/or R1 is xe2x80x94N⊕R4R5R6, or R2 and/or R3 are xe2x80x94N⊕R4R5R6-substituted aryl, wherein R4, R5 and R6 have the meanings cited above, then suitable anions for balancing the positive charge at the xe2x80x94N⊕R4R5R6 group are halides, such as chloride, bromide and iodide, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxy-late, acetate, tosylate or triflat. Bromide, chloride and iodide are preferred.
In those compounds of formula (1) wherein n is 2 or 3, the R groups may have the same or different meanings. The same applies to compounds of formula (1), where m is 2 or 3, with respect to the R1 groups.
Y defined as a 1,2-cyclohexylene radical may be in any of its stereoisomeric cis/trans forms.
Y is preferably a radical of formula xe2x80x94(CH2)rxe2x80x94, wherein r is an integer from 1 to 8, or of formula xe2x80x94C(R4)2xe2x80x94(CH2)pxe2x80x94C(R4)2xe2x80x94, wherein p is a number from 0 to 6, preferably from 0 to 3, and the R4 groups are each independently of one another hydrogen or C1-C4alkyl, preferably hydrogen or methyl, or a 1,2-cyclohexylene radical or a 1,2-phenylene radical of formula: 
Halogen is preferably chloro, bromo or fluoro. Chloro is particularly preferred.
If n or m is 1, the R and R1 groups are preferably in 4-position of the respective benzene ring unless R or R1 is nitro or COOR4. In that case the R or R1 group is preferably in 5-position. If R or R1 is N⊕R4R5R6, the R or R1 group is preferably in 4- or 5-position.
If n or m is 2, the two R or R1 groups are preferably in 4,6-position of the respective benzene ring unless R or R1 is nitro or COOR5. In that case, the R or R1 groups are preferably in 3,5-position.
If R or R1 is di(C1-C12alkyl)amino, then the alkyl group may be straight-chain or branched. The alkyl group preferably contains 1 to 8, more preferably 1 to 3, carbon atoms.
R and R1 are preferably hydrogen, OR4, COOR4, N(R4)2 or N⊕(R4)3, wherein in N(R4)2 or N⊕(R4)3 the R4 groups may be different and are hydrogen or C1-C4alkyl, preferably methyl, ethyl or isopropyl.
R2 and R3 are preferably hydrogen, methyl, ethyl or unsubstituted phenyl.
In particularly preferred compounds of formula (2) R8 is hydrogen.
Aryl is typically naphthyl or, preferably, phenyl.
Particularly interesting compounds for use in the novel process are those of formulae 
The compounds of formula (1) and (2) are known or can be prepared in a manner known per se. General methods of preparation are described, inter alia, in U.S. Pat. No. 5,281,578 and by Bernardo et al. in Inorg. Chem. 35 (1996) 387.
The compounds of formula (1) or (2) can be used singly or in admixture with two or more compounds of formula (1) or (2).
It is also possible to use the compounds of formula (1) or (2) together with transition metal salts or complexes, for example with compounds or salts of manganese, iron, cobalt or copper. Suitable are, for example, the salene complexes which are disclosed in the European patent applications No. 98810870.0 and 98810289.3.
This invention also relates to a washing and cleaning agent, which comprises
I) 5-90%, preferably 5-70%, A) of an anionic surfactant and/or B) of a nonionic surfactant,
II) 5-70%, preferably 5-50%, more preferably 5-40%, C) of a builder substance,
III) 0.1-30%, preferably 1-12%, D) of a peroxide, and
IV) a compound of formula (1) or (2) in an amount which in the washing or cleaning process results in a 1-500 xcexcmolar, preferably 5-350 xcexcmolar, more preferably 10-250 xcexcmolar, solution.
The washing and cleaning agent can be in solid or liquid form, for example in the form of a liquid non-aqueous agent, containing not more than 5% by weight, preferably 0 to 1% by weight, of water, and as basis a suspension of a builder substance in a nonionic surfactant, as is described, inter alia, in GB-A-2,158,454.
However, the washing and cleaning agent is preferably in powdered or granulated form which may be produced, for example, by first preparing a starting powder by spray-drying an aqueous slurry, containing all of the above components except the components D) and E), and then adding the dry components D) and E) and mixing all of the components. It is also possible to add the component E) to an aqueous slurry containing the components A), B) and C) and, after spray-drying this mixture, mixing the component D) with the dry mixture.
It is also possible to start from an aqueous slurry which contains the components A) and C), but not, or only partially, component B). After spray-drying the slurry, the component E) is mixed with the component B) and added thereto, and the component D) is then admixed in dry form.
The anionic surfactant A) may be, for example, a sulfate, sulfonate or carboxylate surfactant, or a mixture thereof. Preferred sulfates are those which contain 12-22 carbon atoms in the alkyl radical, optionally in combination with alkylethoxysulfates, the alkyl radical of which contains 10-20 carbon atoms.
Preferred sulfonates are, for example, alkylbenzenesulfonates containing 9-15 carbon atoms in the alkyl radical. The cation in the anionic surfactants is preferably an alkali metal cation, more preferably sodium.
Preferred carboxylates are alkali metal sarcosinates of formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1, wherein R is alkyl or alkenyl containing 8 -18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl, and M1 is an alkali metal.
The nonionic surfactant B) may be, for example, a condensate of 3-8 mol of ethylene oxide with 1 mol of primary alcohol containing 9-15 carbon atoms.
Suitable builder substances C) are, for example, alkali metal phosphates, preferably tripolyphosphates, carbonates or bicarbonates, more preferably their sodium salts, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates), or mixtures of these compounds.
Particularly suitable silicates are the sodium salts of crystalline sheet silicates of formula NaHSitO2t+1.pH2O or Na2SitO2t+1.pH2O, wherein t is a number from 1.9 to 4, and p is a number from 0 to 20.
Preferred aluminium silicates are those which are commercially available under the names Zeolite A, B, X and HS as well as mixtures containing two or more of these components.
Preferred polycarboxylates are the polyhydroxycarboxylates, in particular citrates, and acrylates as well as their copolymers with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetracetic acid, ethylenediaminedisuccinate both in racemic form and in (S,S)-form.
Particularly suitable phosphonates or aminoalkylenepoly(alkylenephosphonates) are the alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.
Suitable peroxide components D) are, for example, the organic and inorganic peroxides known in the literature and available on the market, which bleach textile materials at the standard washing temperatures, for example from 10 to 95xc2x0 C. The organic peroxides are, for example, mono- or polyperoxides, preferably organic peracids or the salts thereof, such as phthalimidoperoxycapronic acid, peroxybenzoic acid, diperoxy dodecane diacid, diperoxynonane diacid, diperoxydecane diacid, diperoxyphthalic acid or the salts thereof.
However, it is preferred to use inorganic peroxides, such as persulfates, perborates, percarbonates or persilicates. It is of course also possible to use mixtures of inorganic and/or organic peroxides. The peroxides can be in different crystal forms and may have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
The peroxides are preferably added to the washing and cleaning agent by mixing the components, for example by means of a screw feeding system and/or a fluidised bed mixer.
In addition to the novel combination, the washing and cleaning agents may contain one or more than one fluorescent whitening agent, for example from the class of the bis-triazinylaminostilbenedisulfonic acid, bis-triazolylstilbenedisulfonic acid, bis-styrylbiphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative.
The washing and cleaning agents may also contain suspending agents for dirt, for example sodium carboxymethylcellulose, pH-regulators, e.g. alkali or alkaline earth metal silicates, foam regulators, e.g. soaps, salts for regulating the spray-drying and the granulation properties, e.g. sodium sulfate, fragrances and, optionally, antistatic agents and softe ners, enzymes such as amylase, bleaching agents, bleaching activators such as TAED (tetraacetylethylenediamine) or SNOBS (sodium nonanoyloxybenzene sulfonate), pigments and/or shading agents. These components must, of course, be stable against the bleaching agent used.
Other additives preferably added to the novel washing and cleaning agents are polymers which prevent staining during the washing of the textiles through dyes that are present in the liquor and that have separated from the textiles under the washing conditions. These additives are preferably polyvinylpyrrolidones which are unmodified or modified through the incorporation of anionic or cationic substituents, in particular those having a molecular weight in the range from 5""000 to 60""000, preferably from 10""000 to 50""000. These polymers are preferably used in an amount from 0.05 to 5% by weight, preferably from 0.2 to 1.7% by weight, based on the entire weight of the washing agent.